Sulfatoalkylamino derivatives of triazine and pyrimidine vat dyestuff



United States Patent 3,157,653 SULFATOALKYLAMENO DERIVATIVES 0F TRlA- ZINE AND PYRlh/HDINE VAT DYESTUFF Max Staeuhle and Kurt Welter, Basel, and Paul Hugelshater, Uteltingen, Switzerland, assignors to Ciba Limited, Basel, Switzerland, 21 company of Switzerland No Drawing. Filed Nov. 17, 1961, tier. No. 153,203 Claims priority, application Switzerland, Nov. 22, 1960, 13,971/60; Oct. 18, 1961, 12,4i52/61 5 Claims. (Cl. 260-249) This invention provides new vat dyestuffs which contain at least one sulfatoalkylamino group bound to a nucleus containing two nitrogen atoms in a heterocyclic ring or bound to a chlorine-free triazine radical, and which contain at least 4, and advantageously at least 5, fused rings or at least two anthraquinone radicals. The term vat dye-stuffs includes dyestuffs which can be converted by reduction into a so-called leuco compound or vat which has a better aiiinity for natural or regenerated cellulose fibers than the non-reduced form, and which can be reconverted by oxidation into the original chromophoric system. As suitable vat dye-stuffs there may be mentioned more especially those of the anthraquinone series, for example, those which contain an anthraquinone nucleus and also fused rings, especially at least two fused carbocyclic or heterocyclic rings, or which consist of several anthraquinone units, and also vat dyestuffs of the perylene tetracarboxylic acid series. The vat dyestuffs may, of course, contain substituents usual in vat dyestuffs, for example, halogen atoms, alkoxy groups or acylamino groups, but they must contain at least one sulfatoalkylamino group bound to a nucleus containing two nitrogen atoms, in a heterocyclic ring or bound to a chlorine-free triazine ring. Especially valuable are those vat dyestuffs of the kind defined above which contain as the only groups imparting solubility in water one or more sulfatoalkylamino groups containing straight or branched lower alkylene chains.

The invention also provides a process for the manufacture of the aforesaid dyestuffs, wherein a vat dyestuif which contains at least four and advantageously at least five fused rings or at least two anthraquinone radicals and contains a hydroxyalkylamino group bound to a nucleus containing two nitrogen atoms in a heterocyclic ring or bound to a chlorine-free triazine ring, is treated with a sulfating agent.

The vat dyestuffs used as starting materials which contain a hydroxyalkylamino group as defined above can be prepared by condensing a polyhalogenated heterocyclic compound which contains two or three nitrogen atoms in a fiveor six-membered ring, for example, cyameluric acid chloride, cyanuric chloride, cyanuric bromide, trior tetrachloropyrimidine, tetrachloropyridazine, dichloroquinoxaline or the like, on the one hand, With a vat dyestuff or a vat dyestuif intermediate containing an acylatable amino group and at least four, and advantageously at least five, fused rings or at least two anthraquinoneradicals, and, on the other, with a primary or secondary hydroxylamine.

When cyanuric chloride or bromide is used the condensation is carried out in such manner that the resulting product containing a hydroxyalkylamino group contains no halogen in the triazine nucleus.

As vat dyestuffs or a vat dyestuff intermediate containing acylatable amino groups and at least four fused rings or at least two anthraquinone nuclei, there may be men tioned, for example, 4-aminoanthraquinone-2:1(N)-acridone, S-amino-l:9-isothiazole-anthrone, 4- or 5-aminoanthrapyrimidine, amino-acedianthrones, 4- or 5-arnino- 1: l'-dianthrimide-carbazole, 4- or 5-amino-5-be-nzoylamino-dianthrimide-carbazole, 4-amino-4'-benzoylarnino- Patented Nov. 17, 1964 dianthrimide-carbazole, 4 4'-diamino-1 1'-dianthrirnidecarbazole, 4:5 diamino 1:1 dianthrimide-carbazole, 5 :5-diamino l:l'-dinanthrimide-carbazole, 4-aminoanthrapyridone, aminodibenzanthrone, aminoisodibenzanthrone, aminoanthanthrone, aminobenzanthrone, aminofiavanthrone, aminopyranthrone, aminodibenzpyrenequinone, and also compounds of the formulae CH CH3CHQCHCH2OH HzN-CHzOHg-O CHzOECHzOH V NH; NH: 2115 Hz H NE; NH;

The molar ratio of the reactants used in the condensation is advantageously such that for one or two acylatable amino groups of the parent vat dyestuif at least one molecular proportion of the polyhalogenatedcompound is present, and the further halogen atoms in the resulting condensation product are then exchanged by the reaction with the aforesaid hydroxyalkylamines. In the case of triazine condensation products all the halogen. atoms must be exchanged for hydroxyalkylarnino groups.

The sulfating of the hydroxyalkyl groups in the condensation products so obtained may be carried out by the usual methods, for example, by means of concentrated sulfuric acid, advantageously sulfuric acid of strength or oleum of 1 to strength at room temperature or With the application of heat. In certain cases the sulfation may be carried out by means of chlorosulfonic acid, advantageously in a tertiary amine, such as pyridine.

The dyestufis of the invention are suitable for dyeing a very Wide variety of materials, but especially for dyeing or printing textile materials of natural or regenerated cellulose by the dyeing or printing methods customarily used for vat dyestuffs. The dyeings and prints obtained with the dyestuffs of the invention are distinguished by their excellent fastness to light and excellent properties of wet fastness. In general their fastness to soda boiling is also excellent. The dyeings produced with the dyestuffs of the invention are also fast to dry cleaning and migration. The dyed fabrics can therefore be coated with synthetic resins, for example, with polyvinyl chloride, without the dyestutf migrating into the synthetic resin, which is especially important in the production of artificial leather.

The dyestuifs of the invention are generally very easy to vat, in many cases at room temperature, and, if desired, with mild reducing agents, and they possess a very good levelling and through-dyeing power. Owing to the ease with which these dyestulis can be vatted, it is unnecessary to Work them up into finely dispersed powders or pastes.

The following examples illustrate the invention, the parts and percentages being by weight:

Example 1 parts of aminodibenzanthrone (nitrogen content=3.67%) are suspended in 300 parts of dry nitrobenzene, while stirring, and the whole is heated to 160 to 170 C. There is then added a solution of 13 parts of cyanuric chloride in 80 parts of nitrobenzene, 0.5 part of anhydrous pyridine is added, and the Whole is stirred for a further 12 hours at 170 C. After cooling the mixture to C., the product of the cyanuration is isolated by filtration and washed with nitrobenzene. The filter residue isthen introduced in small portions at 150 to 160 C. into 100 parts of monoethanolamine, and the Whole is stirred for 4 hours at 150 C. After cooling the mixture it is poured into water, and the reaction product is isolated by filtration, thoroughly washed with water and acetone, and dried in vacuo at 70 to 80 C.

The dried condensation product is then introduced in small portions into 300 parts of sulfuric acid of 100% strength and the whole is stirred for 4 hours at room temperature. The mixture is then poured into ice water, the dyestuif is filtered oil and Washed with water until the washings are neutral, and the dyestutf is dried in vacuo at 80 C. The new dyestuff of the formula NH-CH CHy-OSO H can be vatted very easily, and dyes cotton and regenerated cellulose from an alkaline hydrosulfite vat blue-green to blue-black tints having very good properties of wet fastness and an excellent fastness to light.

A dyestufi having similar properties is obtained by using for the esterification, instead of the aforesaid quantity of sulfuric acid of strength, an equal quantity of chlorosultonic acid at 0 to 4 C. or the same quantity of ortho-dichlorobenzene containing 27 parts of pyridine and 43 parts of chlorosulfonic acid, and the mixture is heated for several hours at 60 C.

Example 2 25 parts of the condensation product or" 20 parts of aminodibenzanthrone (nitrogen oontent=3.48%) and 13 parts cyanuric chloride are introduced in small portions at 160 to 1'7 0 C., into 200 parts of diethanolamine, and the whole is stirred for 3 hours at that temperature. After cooling the mixture, it is poured on to ice and the reaction product is isolated by filtration, thoroughly washed with water and acetone, and dried in vacuo at 90 C.

The dry condensation product is then slowly introduced into 300 parts of sulfuric acid monohydrate and the Whole is stirred for 3 hours at room temperature. The whole is then introduced into ice water, the dyestuii is isolated by filtration, and it is then washed until the washings are neutral and dried in vacuo at 80 C.

The dyestuli has the probable formula It can be vatted very easily and dyes cotton and regenerated cellulose from a violet hydrosuliite vat blue-grey to blue-black tints having very good properties of wet fastness.

Example 3 9 parts of aminodibenzanthrone (nitrogen content: 21%) are suspended in 200 parts of dry uitrobenzene, While stirring, and the whole is heated to 160 to 170 C. There is then added a solution of 6 parts of 2241516- tetrachloropyrirnidine in 50 parts of nitrobenzene, 0.5 part of pyridine are also added, and the Whole is stirred for 20 hours at C. After cooling the mixture to room temperature, the condensation product is isolated by filtration with suction and washed with nitrobenzene and then with acetone. The filter residue is introduced in small portions, While stirring, at to 150 C. into 100 parts of monoethanolamine, and boiled for 2 hours under reflux. After being cooled, the mixture is introduced into Water, and the reaction product is isolated by filtration, washed with water and then with acetone, and dried in vacuo at 70 C.

can be very easily vatted, and dyes cotton and regenerated cellulose from an alkaline hydrosulfite vat grey tints having very good properties of fastness.

Dyestuffs having similar properties are obtained by using in this example, instead of 2:4:5:6tetrachloropyrimi dine, the equivalent quantity of 2:4:6-trichloropyrimidine of the corresponding quantity of 2:4:6-tribromopyrimidine.

Example 4 5 parts of amino-acedianthrone, 5 parts of cyanuric chloride and 100 parts of dry nitrobenzene are stirred for 8 hours at 170 to 180 C. After being cooled to room temperature, the product is isolated by filtration, washed with nitrobenzene and acetone, and then introduced in small portions into 50 parts of 4-arninobutanol. The suspension is heated for several hours at 110 to 120 C., then cooled, and the reaction product is isolated by filtration. The filter residue is washed With acetone and esterified by being reprecipitated from 20 times its Weight of sulfuric acid of 100% strength at room temperature.

The mixture is then poured into ice water and the dye stuff of the formula is isolated by filtration. The filter residue is pasted with Water and adjusted to the pH value of 8.5 by means of a solution of sodium hydroxide, and the mixture is then evaporated to dryness in vacuo at to C.

The dyestuff dyes cotton and regenerated cellulose from a hydrosulfite vat very fast brown tints.

By using in this example, instead of 4-aminobutanol, the same quantity of N-methyl-ethanolamine or 3-aminopropanol, there are obtained dyestuffs having similar tinctorial properties.

Example 5 7.6 parts of 2-(3-carboxyphenylamino)-4:.5 6-trichloropyrimidine are converted into the corresponding carboxylic acid chloride by being stirred in 100 parts of dry nitrobenzene with 4 parts of thionyl chloride for 2 hours at to 97 C., While stirring well. After the addition of 8.4 parts of amino-acedianthrone and 0.1 part of pyridine, the condensation is carried out for 3 hours at 140 to 150 C., While stirring Well. The brown suspension is cooled, filtered, and the filter residue is Washed with nitrobenzene and then with alcohol and then introduced in small portions into 150 parts of dioxane and 50 parts of N-methylethanolamine. The whole is heated for 3 hours at 100 to C., it is then allowed to cool, and the reaction product is isolated by filtration. The filter residue is washed with dioxane, then with acetone and is esterified by reprecipitation from 15 times its weight of sulfuric acid of 100% strength at 6 to 8 C. The sulfuric acid mixture is poured on to ice water, and the dyestufi" is isolated by filration. The filter residue is pasted With a small amount of water, then adjusted to a pll-I'value of 8 with sodium hydroxide solution, and dried in vacuo at 60 C. The dyestutt of the formula dyes cotton and regenerated cellulose fast brown tints from an alkaline hydrosulfite Vat.

The 2-(3'-carboxy phenylamino) 4:5 :6 trichloropyrimidine used in this example can be prepared, for example, by heating for 4 hours at '70 m7 C. an aqueous alcoholic solution of 50% strength of an equimolecular mixture of the sodium salt of E-aminobenzoic acid and 2:4:5 G-tetrachloropyrimidine, and the product is obtained in the form of colorless needles melting at 203 to 205 C.

By using in this example, instead of 2-(3-carboxyphenylarnino)-4:5:6-trichloropyrimidine, an equivalent quantity of 2-(4'-carboxy phenylamino) 4:6 dichlorol :3 S-triazine or 2-(4'-carboxyphenylamino)-4-amino-6- chloro-1z3z5-triazine, there are obtained dyestuifs having similar properties.

Example 6 6.2 parts of 2-(4-carboxyphenylamino)-4:6-dichloropyrimidine are converted into the carboxylic acid chloride in 100 parts of dry nitrobenzene with 4 parts of thionyl chloride, while stirring and heating at 90 to 100 C. After the addition of 0.1 part of pyridine, 6.8 parts of 4-aminoanthraquinone-2:1(N)-acridone are introduced, and condensation is brought about for 2 hours at 120 to 125 C.

and then for a further hour at 14-5 to 150 C. After the mixture has been cooled, the acylation product is isolated by filtration, washed with alcohol and then stirred in small portions into 100 parts of monoethanolamine. The whole is heated for 3 hours at 110 C., and is then cooled and introduced into ice water. The reaction product is filtered off, washed with water and then with acetone, and dried. For esterification the dry powder is introduced into 100 parts of sulfuric acid of 100% strength, the mixture if stirred for 2 hours at 4 to 8 C., and then poured on to ice water, and the dyestuff is isolated by filtration. The filter residue is pasted With a small amount of water, adjusted to a pH-value of 8 with sodium hydroxide solution and then evaporated to dryness in vacuo at 60 C.

The dyestulf so obtained has the formula =0 IIIH-OHzCHrOSOgNH H N 0 Nn-ocO-d C-NH-OH CH -OSO Na quantity of 2-(4'-carboxyphenylarnino) -4-rnethyl-6-cl1loropyrirnidine, which can be obtained by heating an aque- 531 ous alcoholic solution of 50% strength of 4-amino-benzoic acid and 2:6-dichloro-4-methylpyrimidine, there is obtained a dyestuff having similar properties.

Example 7 685 parts of 2-(3-carboxyphenylamino)-426-dichloro- 1:3:5-triazine and 5 parts of thionyl chloride in 150 parts of dry nitrobenzene and 0.2 part of pyridine are stirred and heated at to C. in the course of 2 to 3 hours, whereby the corresponding carboxylic acid chloride is obtained. The excess of thionyl chloride is distilled off in vacuo, then 4.6 parts of 5:5'-diamino-1:l'-dianthrimide-carbazole are added, and condensation is carried out for 4 hours at to C. and then for a further 6 hours at 170 to 130 C. After cooling the mixture the acylation product is isolated by filtration, washed with nitrobenzene and then acetone, and then introduced in small portions into parts of Z-aminoethanol. The brown suspension is stirred for 4 hours at 105 C. After being cooled, the mixture is introduced into ice water, and the reaction product is isolated by filtration, washed until the washings are neutral, and dried. For esterification the dry powder is introduced into 100 parts of sulfuric acid of 100% strength, and the mixture is stirred for 4 hours at 5 to 9 C., and is then worked up in the usual manner.

The resulting dyestuif of the formula NH-C 112 O I-Ir-O S O Na can easily be vatted, and dyes cotton and regenerated cellulose very fast yellow-brown tints.

Example 8 6.9 parts of 4:5'-diamino-1:1'-dianthrimide carbazole are heated in 250 parts of nitrobenzenc with 12.5 parts of cyanurie chloride and 1.0 part of pyridine for 16 hours at to C., While stirring. After being cooled, the red-brown suspension is filtered, and the filter residue is Washed with nitrobenzene. The filter residue,

while moist with nitrobenzene, is then suspended in 200 parts of dioxane, and the mixture is heated with 25 parts of 2-amino-2-methyl-1:3-propaue-diol to 100 C., while stirring. The mixture is then maintained for 6 hours under reflux, and the reaction product is then isolated by filtration. The filter residue is washed with dioxane and dried in vacuo at 80 C.

For esterification the pulverized product is introduced in small portions into 150 parts of oleum containing 5% of sulfur trioxide, and the mixture is stirred for 3 hours, and

' it) then poured cautiously on to ice water. The new dye- The dried product is then pulverized, and introduced stuff so obtained has the formula in small portions into 150 parts of oleum containing 2% OIIs-l-CHZOSOSH CH OSOsEI and is isolated by filtration, and converted into its sodium of sulfur trioxide, While stirring, at 4 to 8 C. The mixsalt by neutralizing the filter residue With dilute sodium hyture is further stirred at that temperatur r 3 hours, h'oxide sohl'iigr and is then poured on to ice. The dyestuif is isolated The d t if is easily Soluble in the Vat, and dyes from the suspension by filtration, and is cautiously Washed ton and regenerated Cellulose Very fast brown tinm with Water until dlssolution begins. The filter residue v is then pasted with a small amount of water, adjusted 2 using l i i to a pH value of 8 with a dilute solution of sodium hy- Propane we quann y 0 u we or droxide, and the dyestuif is salted out by the addition of Z-arninQ-Z methyI-l-propanol or 'tris-(hydr0x ymethy1)- sodium chloride. The dyestuff is filtered off, pressed aminomethane, dyestuffs having similar properties are ob- 11, d d i d i ague t 70 C tained. The dyestuif of the formula (I) HbITOC CONH (6 NaO S0CII CH l |TH NH-GHzCH2OSO Na N/ N l H i HN b /ii-HN 0 ii 1 IH-(i\ C-N Naoaso omilm N N H OH OSO Na Example 9 is soluble in Water and dyes cotton and regenerated cel- 6.1 parts of the dyestuff intermediate product of the M1036 from an alkaline hydrosulfite Vat fast brown formula yellow tints.

Example 10 6.8 parts of 2-(4'-carboxyphenylamino )-4-amino-6- O 0 chloro-1:3:5-triazine are suspended in 200 parts of dry II I I ll nitrobenzene and 1.0 part of dimethylformamide, and 6.0 parts of thionyl chloride are added, While stirring. The Whole is then heated at 90 to 100 C. until a clear solution of the acid chloride is obtained. There are I I H I then introduced 6.1 parts of the dyestuft intermediate of rnN o 0 N11. the formula which can be obtained by condensing 1 mol of isophthalic acid dichloride with 2 mols of l-amino-S-nitro-anthraquinone followed by reduction, are dissolved at the boil in 200 parts of dry nitrobenzene. The brown-red solution is allowed to cool to 170 C., and a solution of 6.0 parts HNOC CONH of cyanuric chloride in 50 parts of nitrobenzene is then I i added. After the addition of 0.2 part of dry pyridine, condensation is carried out for 9 hours at 170 to 180 C.,

then the mixture is allowed to cool, and the product is isolated by filtration. it is Washed with acetone and dried at 40 C. in vacuo. HQN O 9.0 parts of the product so obtained are then introduced at room temperature into 150 parts of monoethanolarnine, 7Q

and the whole is heated for 3 hours at to C., and the latter is acylated for 3 hours at to C. while stirring. After cooling the reaction mixture it is and then for 2 hours at C. After cooling the mixpoured on to ice, the reaction product is isolated by filtrature, the acyiation product is isolated by filt'ration, washed tion, washed with Water until the washings are neutral, with acetone, and introduced into 100 parts of N-methyland dried in vacuo at 70 C. 75 ethanolamine. The Whole is heated for 4 hours at 100 It i to 110 C., while stirring, then cooled, poured into ice water, and the reaction product is isolated by filtration, Washed with water and died in vacuo at 70 C.

For esterification the dyestutf is introduced in small portions into 150 parts of sulfuric acid of 100% strength at 4 to 8 C., the whole is stirred for 3 hours, and is then poured on to ice. The dyestutl has the formula and is filtered off, and converted into its sodium salt by cautiously neutralizing the filter residue with sodium hydroxide solution. The product is dried in vacuo at to C. I

The dyestuff dyes cotton and regenerated cellulose reddish yellow tints having very good properties; of fastnes s.

Example 11 stirred at that temperature for a further 3 hours. After cooling the mixture, the condensation product is filtered off, washed with nitrobenzene and then with alcohol, and suspended in parts of diethanolamine. The suspension is heated at U0 (3., for 3 hours while stirring, and, after being cooled, the mixture is poured on to ice water. The reaction product is filtered oif, Washed with water, and dried.

The dried pulverized product is then introduced in small portions into parts of sulfuric acid of 100% strength at, 4-8" C. while stirring, and the whole is stirred for 4 hours at that temperature. The mixture is then poured on to ice. The suspension of the yellow-brown dyestuif is then filtered-and the filter residue is washed with water dyes cotton and regenerated cellulose from an alkaline hydrosulfite vat orange-yellow tints having very good properties of fastness.

What is claimed is:

l. A vat dye of the formula DNHX wherein D is dibenzanthrone and X is a member selected from the group consisting of the pyrimidine and the 1:3:5-triazine radical bound through one of its carbon atoms to the NH-bridge and hearing at two of its further carbon atoms a lower 'sulfatoalkyl-arnino group bound by its amino nitrogen atom, the fourth carbon atom of the pyrimidine nucleus bearing a member selected from the group consisting of the chlorine and the lower sulfatoalkylarnino substituents.

2. The dyestuffs of'clairn 1, wherein the lower sulfatoalkylarnino group is fi-sulfatoethylamino.

3. The vat dyestutt of the formula V 4. The vat dyestuff of the formula 5. The vat dyestufi of the formula References {jihad in the file of this patent UNITED STATES PATENTS Scheyer et a1. June 2, 1936 Hentrich et a1. Oct. 13, 1942 DAlelio June 30, 1945 Moergeli Sept. 11, 1951 Randall et a1. Apr. 17, 1956 Brassell et a1 Dec. 11, 1956 Sutter June 24, 1958 Heslop Oct. 6, 1959 Heslop et a1. May 3, 1960 Staeuble et a1 Feb. 20, 1962 Putter et a1 Apr. 10, 1962 Wegmann et a1 July 10, 1962 Staeuble et a1 Sept. 18, 1962 FOREIGN PATENTS France Oct. 24, 1960 OTHER REFERENCES Wegrnann: Textil-Praxis, October 1958, page 1056. 

1. A VAT DYESTUFF OF THE FORMULA D-NHDX WHEREIN D IS DIBENZANTHRONE AND X IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF THE PYRIMIDINE AND THE 1:3:5-TRIAZINE RADICAL BOUND THROUGH ONE OF ITS CARBON ATOMS TO THE -NH-BRIDGE AND BEARING AT TWO OF ITS FURTHER CARBON ATOMS A LOWER SULFATOALKYL-AMINO GROUP BOUND BY ITS AMINO NITROGEN ATOM, THE FOURTH CARBON ATOM OF THE PYRIMIDINE NUCLEUS BEARING A MEMBER SELECTED FROM THE GROUP CONSISTING OF THE CHLORINE AND THE LOWER SULFATOALKYLAMINO SUBSTITUENTS. 